Performance of fluorene and terthiophene copolymer in bilayer photovoltaic devices: The role of the polymer conformations

We report experiments using fluorene and terthiophene copolymer as the active layer in bilayer devices with C60. The highest short circuit current, open circuit voltage and power conversion efficiency upon AM1.5 illumination were 6.8 mA/cm2, 0.68 V and 2.33%, respectively. Density functional theory analysis was used to identify the most stable configurations of the terthiophene moieties in the polymer: the most stable form has the thiophene rings in the alternate configuration (anti) and the second conformation has the thiophene rings pointing to the same direction (syn). Comparing theoretical results with measurements of absorbance, X-ray diffraction, and X-ray reflectometry experiments, we conclude that the annealing treatment produces conformational anti to syn transition along the backbone of poly[9,9′-n-dihexyl-2,7-fluorene-alt-2,5-terthiophene] (LaPPS45). The syn segments of the chain condensed then in a lamellar ordered structure which increases the degree of crystallinity of the annealed samples and improve the light harvest at long wavelengths. From absorption measurements of films submitted to different annealing temperatures and with the help of theoretical calculations we propose a “wave-like” aggregation pattern to the syn segments in those lamellas.

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► We report experiments using fluorene and terthiophene copolymer in bilayer devices with C60.
► We identify the most stable configurations of the terthiophene moieties in the polymer.
► The annealing treatment produces conformational anti to syn transition along the backbone.
► The syn segments of the chain condensed in a lamellar ordered structure.
► We propose a “wave-like” aggregation pattern to the syn segments in those lamellas.